WO2005076389A2 - Anodes autoporteuses a film mince de type a alliage destinees aux batteries a ions de lithium - Google Patents

Anodes autoporteuses a film mince de type a alliage destinees aux batteries a ions de lithium Download PDF

Info

Publication number
WO2005076389A2
WO2005076389A2 PCT/US2004/043445 US2004043445W WO2005076389A2 WO 2005076389 A2 WO2005076389 A2 WO 2005076389A2 US 2004043445 W US2004043445 W US 2004043445W WO 2005076389 A2 WO2005076389 A2 WO 2005076389A2
Authority
WO
WIPO (PCT)
Prior art keywords
layer
cavities
electrode
battery
forming
Prior art date
Application number
PCT/US2004/043445
Other languages
English (en)
Other versions
WO2005076389A9 (fr
WO2005076389A3 (fr
Inventor
Prashant N. Kumta
Jeff Maranchi
Moni Datta
Original Assignee
Carnegie Mellon University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carnegie Mellon University filed Critical Carnegie Mellon University
Publication of WO2005076389A2 publication Critical patent/WO2005076389A2/fr
Publication of WO2005076389A9 publication Critical patent/WO2005076389A9/fr
Publication of WO2005076389A3 publication Critical patent/WO2005076389A3/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0414—Methods of deposition of the material by screen printing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
    • H01M4/0485—Casting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0492—Chemical attack of the support material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Li-ion batteries are at the forefront of battery technology, there is an ever-growing need to improve the energy density as devices shrink in size to dimensions unimaginable even five years ago.
  • Lithium metal has been widely used as the anode material in lithium-ion batteries because lithium ion is the lightest cation (other than H + ) and is a highly mobile species. Lithium metal is also highly desirable because it can deliver a high theoretical energy density (3860 mAh/g) compared to graphite, the conventional anode material, LiC 6 (372 mAh/g). Many attempts have been made to fabricate and commercialize rechargeable batteries containing Li metal anodes, including an attempt by Nippon Telephone and Circuit (NTT) Corporation using a lithium metal anode and amorphous V 2 O 5 cathode. J. Yamaki and S. Tobishima in Handbook of Battery Materials, ed. by J.
  • Lithium metal anodes tend to form dendritic structures gradually after a repeated number of charge discharge cycles.
  • the dendrites can cause a short circuit condition between the anode and cathode resulting in failure of the cell.
  • the lithium dendrites can also be broken off during cycling and coated with an insulating solid-electrolyte interfacial (SEI) layer (E. Peled, J. Electrochem.
  • lithium insertion materials M. Armand, in Materials for Advanced Batteries, ed. by D. Murphy, J. Broadhead and B. Steele, Plenum Press, New York, p. 145 (1980); B. Scrosati, J. Electrochem. Soc, 139, 2776 (1992)
  • lithiated carbons have been the most promising and hence most widely studied and used.
  • the carbon based anodes have lower redox potentials than polymers, metal oxides, or chalcogenides.
  • the carbon based anodes also have better dimensional stability than lithium alloys. Furthermore, the carbons are relatively cheap and abundant. M. Winter and J. Besenhard in Handbook of Battery Materials, ed. by J. Besenhard, Wiley-VCH, Weinheim, 1999.
  • the electrochemical response of carbon based anodes depends on the structure of the parent carbonaceous material, the type of electrolyte, and the interactions between the electrolyte and the anode.
  • graphite is actually reserved for carbons that have perfect AB (hexagonal graphite, more common) or perfect ABC (rhombohedral graphite, less common) layer stacking.
  • a pure single polytype of graphite is difficult to obtain because the free energies associated with the AB and ABC polytypes are very close in value.
  • the typical process of lithium intercalation into graphitic carbons is called 'staging' (J. Dahn, Phys. Rev. B, 44, 9170, (1991)) in which the ABA layers slide and form an AAA configuration, as shown in Fig.l.
  • Graphitic carbons have a theoretical maximum capacity of 372 mAh/g.
  • the first charge cycle typically exceeds 372 mAh/g due to the SEI formation and corrosion-like reactions of Li x C ⁇ .
  • Non-graphitic carbons are also potentially attractive anode materials for two reasons.
  • the cross-linking in non-graphitic carbons between graphene layers tends to prevent co- intercalation of solvent molecules.
  • Lithium alloys were first considered as possible anode materials by researchers working on molten salt electrolyte batteries that operated at temperatures in excess of 400°C. R. Huggins in Handbook of Battery Materials, ed. by J. Besenhard, Wiley-VCH, Weinheim, 1999. Two major alloy systems were studied, the Li-Al (N. Yao, L. Heredy and R. Sauders, J. Electrochem. Soc, 118, 1039 (1971); E. Gay, J. Electrochem. Soc, 123, 1591 (1976)) and Li-Si (S. Lai, J. Electrochem. Soc, 123, 1196 (1976); R. Sharma and R. Seefurth, J. Electrochem.
  • Lithium alloy anode materials have not been commercialized due to the large scale volume expansion and contraction observed in these zintl phase alloys during cycling which results in crumbling and mechanical degradation. Id. In essence, the volume changes create high stresses within the lithium alloy anode material, eventually leading to fracture, pulverization, and subsequent loss of electrical contact between the pulverized particle and the rest of the electrode. After the initial loss of electrical contact, the particle remains virtually inactive for the rest of the useful life of the battery. On a large scale, the degradation can lead to a swift decline, even after only a few cycles.
  • the first cycle reduction of the oxide materials to form tin clusters results in irreversible capacities as high as ⁇ 50% of the total capacity.
  • researchers have attempted to synthesize nanocomposite structures either ex-situ prior to insertion of lithium or in-situ during the insertion of lithium ions similar to the tin oxide glasses.
  • the electrochemically active material is contained within an electrochemically inactive but electrically conducting matrix that serves to withstand the large stresses generated, thereby acting as a 'glue' holding the active material.
  • the electrochemically inactive phase is thermodynamically and chemically stable with respect to the active species while in the latter, the matrix phase is generated by electrochemical reduction and phase separation.
  • IS. Kim, G.E. Blomgren and P.N. Kumta "Si/SiC Nanocomposite Anodes Synthesized using High-energy Mechanical Milling", J. of Power Sources, 130 (2004) 275-280; IS. Kim and Prashant N. Kumta, "High Capacity Si/C Nanocomposite Anodes for Li-ion Batteries", J. of Power Sources 136 (2004) 145-149; IS. Kim, G.E. Blomgren, and P.N.
  • amorphous silicon can be contained within nanocrystalline matrices of TiN, TiB 2 and SiC to successfully stabilize reversible capacities up to 400 mAh/g.
  • Research in bulk lithium alloy anodes has been steadily evolving and appears to be quite promising over that reported in the last 20 years. However, much research still needs to be done to harness the high theoretical capacities of silicon and tin based alloy anodes into realizable practical capacities.
  • SnO 2 thin film anodes have been synthesized by several methods for use in thin film lithium-ion batteries. Low-pressure chemical vapor deposition has been used to produce thin films of SnO 2 which cycled well out to -120 cycles. T. Brousse, R. Retoux, U. Herterich, and D.M. Schleich, J. Electrochem. Soc, 145(1), 1 (1998); R. Retoux, T. Brousse, and D.M. Schleich, J. Electrochem. Soc, 146(7), 2472 (1999).
  • the electrochemical properties of sputter deposited SnO 2 anode thin films were investigated by Nam et al. S.C. Nam, Y.S. Soon, W.I. Cho, B.W.
  • Electron beam evaporation has also been used to fabricate thin film SnO 2 and Si doped SnO 2 anodes.
  • An amorphous silicon tin oxynitride (SiTON) thin film anode was also synthesized by rf magnetron sputtering.
  • SiTON amorphous silicon tin oxynitride
  • a US patent application publication no. 2002/0048705 Al, Apr. 25, 2002 outlined the idea of using silicon-silver thin film multilayer anodes for lithium-ion battery applications.
  • good reversibility was seen out to 100 cycles.
  • Si-Zr thin film anodes have shown promise at lower Si/Zr compositions (Sio. 6 Zr 0 . 4 ).
  • S. Lee, H. Lee, H. Baik, and S. Lee Journal of Power Sources, 119-121, 113 (2003).
  • Ag multilayer thin films also highlighted the fact that Si based systems can show good reversibility for 70 cycles with a reversible capacity of- 17 ⁇ Ah-cm ⁇ - ⁇ m "1 ' S. Lee, H. Lee, Y. Park, H. Baik, and S. Lee, Journal of Power Sources, 119-121, 117 (2003).
  • the same group also showed the positive effect of annealing on the electrochemical cyclability of Co-Si alloy thin films.
  • Y. Kim, H. Lee, S. Jang, S. Lim, S. Lee, H. Baik, Y. Yoon, and S. Lee Electtochimica Acta, 48, 2593 (2003).
  • Si multilayer thin film anodes have also exhibited excellent reversible capacities up to 50 cycles.
  • J. Kim, H. Lee, K. Lee, S. Lim, and S. Lee Electrochem, Comm, 5, 544 (2003).
  • S. Lee, H. Lee, H. Baik, and S. Lee Journal of Power Sources, 119- 121, 113 (2003); S. Lee, H. Lee, Y. Park, H. Baik, and S. Lee, Journal of Power Sources, 119- 121, 117 (2003); Y. Kim, H. Lee, S. Jang, S. Lim, S. Lee, H. Baik, Y. Yoon, and S.
  • Fig. 2 displays the experimental cycling data for sputtered 250 nm and 1 ⁇ m a-Si thin films. Id.
  • An electrically conductive substrate is provided upon which one or more layers of active materials, i.e. materials that react reversibly with the charge carriers in an electrolyte, are formed.
  • the active materials may be chosen from a group consisting of silicon, tin, germanium, indium, antimony, lead, aluminum, magnesium, calcium, bismuth, arsenic, silver, gold, platinum, cadmium, zinc, phosphorus, sulfur and their alloys. Carbon may be used, as needed, as a buffer layer. Certain materials, such as iron, titanium and chromium, may be used as adhesion layers.
  • a layer of chromium may be used as an adhesive layer between a copper substrate and a layer of carbon.
  • the substrate Prior to formation of these layers, the substrate is patterned so as to contain cavities.
  • the active materials, as well as any adhesion and buffer layers, are then formed in one or more layers so that the total cumulative height of the layers is no more than, in one embodiment, one-third of the total depth of each of the cavities.
  • the remaining "unfilled" depth of the cavities provides suitable room for volumetric expansion and contraction of the active materials, resulting in little or no net volume change in the anode at any point during the cycling of the batteries.
  • This anode structure can be fabricated independently of the other manufacturing processes used for creation of the batteries and can therefore be used as a "drop in" component during the battery manufacturing process.
  • FIG. 1 A is a representation of the structure of fully lithiated graphite (LiC 6 ) while FIG. IB illustrates the inplane distribution of the lithium ions in LiC 6 ;
  • FIG. 2 is a comparison of galvanostatic cycling of sputtered 250 nm and 1.0 ⁇ m Si films on Cu foil (both at -C/2.5 rate);
  • FIG. 3 illustrates a portion of a copper substrate;
  • FIG.4 illustrates the substrate of FIG. 3 after a layer of resist has been formed and patterned
  • FIG. 5 illustrates the substrate of FIG. 4 after a hard mask has been formed
  • FIG. 6 illustrates the substrate of FIG. 5 after the remainder of the resist has been stripped leaving a patterned hard mask; the substrate is then subjected to a directional copper etch;
  • FIG. 7A is a top plan view of the substrate after the copper etch while FIG. 7B is a close up of the pattern of cavities formed in the top surface of the substrate;
  • FIG. 8 is a cross-sectional view taken along the lines VIII - VI3I in FIG. 7B;
  • FIG. 9 illustrates the substrate of FIG. 8 after a layer of chromium is formed;
  • FIG. 10 illustrates the substrate of FIG. 9 after a layer of carbon and a layer of silicon are formed;
  • FIG. 11 illustrates the substrate of FIG. 10 after the remainder of the hard mask is stripped;
  • FIG. 12 illustrates a battery constructed with the anode of the present disclosure
  • FIG. 13 illustrates electrochemical cycling data of an as-deposited 50 nm C/ 250 nm
  • FIG. 14 illustrates electrochemical cycling data of an as-deposited 50 nm C/ 250 nm
  • FIG. 15 illustrates electrochemical cycling data of an as-deposited 250 nm Si/50nm
  • FIG. 16 illustrates electrochemical cycling data of a 300°C-4h annealed 250 nm
  • FIG. 17 illustrates electrochemical cycling data of a 500°C-4h annealed 250 nm
  • FIG. 18 illustrates SEM images of a 500°C-4h annealed 250 nm Si/50nm C/10 nm
  • An anode for a lithium ion battery can be constructed as will be described in detail below.
  • a substrate of an electrically conductive material such as polycrystalline copper
  • the pattern can be created by standard industrial processes such as photolithography and rapid ion etching.
  • the patterns will generally consist of cavities, which may have cross-sectional shapes such as squares, rectangles, circles, or of other shapes or combinations of shapes.
  • the dimensions of these patterns may conveniently be on the order of from about 1 ⁇ m to about 10 mm, although there is conceptually no limit placed upon their sizes.
  • One method of depositing thin film layers of these materials is by sputter deposition. Other methods could also be used such as, for example, pulsed laser deposition (PLD), chemical vapor deposition (CVD), plasma enhanced CVD, ion assisted sputter deposition etc.
  • PLD pulsed laser deposition
  • CVD chemical vapor deposition
  • plasma enhanced CVD ion assisted sputter deposition etc.
  • a heat treating step may be performed after the layers are formed, or at intermediate steps before formation of all the layers, as needed for stabilization. For example, a heat treatment after formation of all the layers described above (chromium/carbon/silicon) for a minimum of three hours at 300° C may be performed.
  • Anodes may be created in this fashion so that they constitute a "drop-in" component in the fabrication of the batteries.
  • the anode of this disclosure therefore greatly simplifies the manufacture of lithium-ion batteries by eliminating the use of conventional graphite/binder/carbon black slurry casting of anodes.
  • the anodes described herein are expected to find use in conventionally fabricated lithium-ion cells using both liquid and polymer gel electrolytes.
  • This invention may reduce the volume of the anodes used in lithium-ion batteries while maintaining excellent electrochemical properties such as cycle life, capacity, rate capability, and discharge profile. It may also find applicability in battery types other than lithium-ion batteries.
  • FIG. 3 illustrates a portion of an exemplary substrate 10 which may be, for example, a polycrystalline copper.
  • the substrate 10 has a layer of resist 12 formed thereon and patterned as shown in FIG. 4.
  • the word "formed” as used herein is intended to be used in its broad sense and to encompass any process step or steps which facilitate the creation of the layer.
  • the resist 12 may be any commercially available photo resist, either positive or negative.
  • FIG. 5 illustrates the substrate of FIG. 4 after a hard mask has been formed.
  • the hard mask may be, for example, a layer of silicon dioxide 14 formed using any convenient technique. Thereafter, the remaining photo resist 12 is stripped removing the silicon dioxide 14 above it, leaving the pattern of silicon dioxide 14 illustrated in FIG. 6.
  • a unidirectional etch selective for copper is performed to create wells or cavities 16 as represented by the dotted lines in FIG. 6. The resulting pattern of etched cavities is illustrated more clearly in FIGs. 7A, 7B and 8.
  • FIG. 8 is a cross-sectional view taken along the lines Vm-VIH in FIG. 7B.
  • the pattern can be created using standard industrial processes such as photolithography and rapid ion etchings.
  • the pattern shown in the illustrated example is substantially square or rectangular, other types of patterns such as circles, other shapes, or combination of shapes can be created.
  • Typical dimensions for the cavities are on the order of l ⁇ m to about ten millimeters, although there is conceptually no limit placed upon the size of the cavities or the spacing between the cavities.
  • the layers are constructed of materials chosen from a group consisting of silicon, tin, germanium, indium, antimony, lead, aluminum, magnesium, calcium, bismuth, arsenic, silver, gold, platinum, cadmium, zinc, phosphorus, sulfur and their alloys.
  • the criteria for selecting materials from which active layers are to be formed is that the material must react with lithium, in the case of a lithium battery, in a reversible manner.
  • Other layers may be formed. For example a carbon layer may be used as a buffer layer and layers of chromium, titanium and/or iron may be used as adhesive layers.
  • the first layer may be, for example, an adhesive layer 18 of chromium 10 - 50 nm thick.
  • the layer of chromium 18 may be formed in any conventional manner.
  • a buffer layer 20 of carbon 10 - 50 nm thick may be formed followed by a 250 nm thick active layer of silicon 22.
  • the substrate 10 may be cleaned so as to leave only the material formed in the well in place, or cleaning may wait until all of the steps are performed. In that case, the remainder of the hard mask 14 is stripped off together with any other material formed on the surface thereof.
  • the dimensions given here are exemplary and are directed to the presently preferred embodiment although it is anticipated that other dimensions may provide comparable results as well as other layers of active materials with or without buffer and adhesion layers.
  • the figures are not to scale, in the disclosed embodiment, one will usually not fill more than one third of the total depth of the wells 16. Partially filling the wells to any depth less than completely full is intended to allow room for the expected volumetric expansion and contraction of the formed layers during battery cycling. Because the volumetric expansion and contraction of the formed layers of materials will not exceed the height of the wells 16, there will be no net volume changed in the anode/substrate 10 at any point during cycling of the patterned thin film anodes.
  • One method of forming the various layers of thin films is by sputter deposition, although other methods may be used. One may advantageously deposit multiple layers from the materials identified above in thin films in an alternating fashion.
  • FIG. 12 illustrates a battery constructed using the anode of the present invention.
  • the battery is a lithium battery
  • the concepts of the present invention may be employed in the construction of other types of batteries.
  • the construction of the anode of the present disclosure namely forming wells or cavities of active material, may be useful in the construction of cathodes in such other batteries.
  • FIG. 12 a battery 28 constructed according to the teachings of the present invention is illustrated.
  • the battery 28 has a first terminal 30 connected to an anode 32 constructed according to the teachings of the present disclosure. Because anodes constructed according to the present disclosure greatly simplify the manufacturing of lithium-ion batteries by eliminating the use of conventional graphite/binder/carbon black slurry casting of anodes, the anodes of the present disclosure may constitute a drop-in component.
  • the battery 28 also comprises a second terminal 36 electrically connected to cathode 38.
  • An electrolyte 42 is positioned between the anode 32 and cathode 38 and may be either a liquid or polymer gel electrolyte.
  • the anode may be formed using a variety of different materials which react reversibly with lithium, the selection of the material for cathode 38 and the electrolyte 42 will depend upon the material selected for anode 32. It is anticipated that the selection of an appropriate cathode 38 material and an appropriate electrolyte 42 once the material for the anode 32 has been selected is known in the art need not be repeated here. Finally, the various components comprising the battery 28 are housed within a casing 40. Experimental results
  • FIG. 13A reveals that the C/Si/C sandwich sample starts off with a very high reversible capacity of- 5144 mAh/cc in the 2 nd cycle which fades slowly to - 4450 mAh/cc by the 100 th cycle. Therefore, the capacity fade is 0.14% per cycle.
  • Fig. 13B shows differential capacity plot for the C/Si/C sample cycled at a 0.4C rate. The dQ/dV graph is very similar to those observed before for Cu/Si samples with broad peaks indicating the amorphous nature of the reacting constituents and resultant phases.
  • Fig. 14A shows the effect of increasing the cycling rate by a factor of two to 0.8C.
  • the initial reversible capacity was 5088 mAh/cc which faded to 4277 mAh/cc in the 100 th cycle, resulting in a capacity fade of 0.16% per cycle. Therefore, increasing the C-rate by a factor of two led to a slight increase in the capacity fade, but in general did not change the electrochemical characteristics substantially.
  • the differential capacity plot shown in Fig. 14B for the 0.8C sample shows similar reaction peaks to the slower rate sample shown in Fig. 13B.
  • Fig. 15 A shows that the initial reversible capacity of 6244 mAh/cc was higher than previously reported for the C/Si/C sample.
  • the capacity fade per cycle also increased to 0.21% for the first 100 cycles.
  • the differential capacity graph shown in Fig. 15B also showed consistent electrochemical signatures when compared to the dQ/dV plots shown in Fig. 13B and Fig. 14B.
  • Another strategy to enhance the reversible capacity, while maintaining low fade per cycle was developed.
  • a post-deposition anneal may enhance adhesion between the material layers.
  • Fig. 16B The differential capacity graph shown in Fig. 16B was consistent with the dQ/dV plots shown in Figs. 13B, 14B and 15B.
  • Fig. 17A reveals that the initial reversible capacity was 5379 mAh/cc and the 100 th cycle reversible capacity was 4737 mAh/cc. The capacity fade was excellent at 0.12% per cycle.
  • the Cu/Si samples showed very straight compressive type failures, whereas the annealed samples exhibit a telephone-cord like compressive failure crack morphology.
  • the annealing step may influence the state of stress in the film, as well as change the mechanical properties of all the constituent film layers as well as the Cu substrate.
  • the excellent reversibility and high capacity of the annealed multilayer film illustrates the promise and potential of such thin film anode systems, justifying substantial future research endeavors.

Abstract

L'invention porte sur un substrat conducteur d'électricité sur lequel sont formées une ou plusieurs couches de matériaux actifs, c'est-à-dire de matériaux qui fonctionnent de manière réversible avec les porteurs de charge d'un électrolyte. Avant la formation de ces couches, le substrat reçoit un motif qui contient des cavités. Les matériaux actifs sont ensuite formés dans une ou plusieurs couches de manière à ce que le poids cumulatif total des couches soit inférieur à la profondeur totale de chacune des cavités. La profondeur restante 'non remplie' des cavités laisse suffisamment d'espace pour chacune des cavités. Cette profondeur restante 'non remplie' des cavités assure suffisamment d'espace pour la dilatation et la contraction volumétriques des matériaux actifs, ce qui fait en sorte que le changement de volume dans l'anode à n'importe quel moment du cycle de fonctionnement des batteries soit faible ou nul.
PCT/US2004/043445 2003-12-23 2004-12-23 Anodes autoporteuses a film mince de type a alliage destinees aux batteries a ions de lithium WO2005076389A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53231803P 2003-12-23 2003-12-23
US60/532,318 2003-12-23

Publications (3)

Publication Number Publication Date
WO2005076389A2 true WO2005076389A2 (fr) 2005-08-18
WO2005076389A9 WO2005076389A9 (fr) 2005-10-27
WO2005076389A3 WO2005076389A3 (fr) 2006-05-04

Family

ID=34837342

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/043445 WO2005076389A2 (fr) 2003-12-23 2004-12-23 Anodes autoporteuses a film mince de type a alliage destinees aux batteries a ions de lithium

Country Status (1)

Country Link
WO (1) WO2005076389A2 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1936722A2 (fr) * 2006-12-21 2008-06-25 Commissariat à l'Energie Atomique Accumulateur au lithium comprenant un ensemble collecteur de courant-électrode avec des cavités d'expansion et procédé de fabrication
US7816031B2 (en) 2007-08-10 2010-10-19 The Board Of Trustees Of The Leland Stanford Junior University Nanowire battery methods and arrangements
WO2010129866A1 (fr) * 2009-05-08 2010-11-11 Robert Bosch Gmbh Batterie lithium-ion avec réservoir à volume variable
WO2012084570A1 (fr) * 2010-12-21 2012-06-28 Sgl Carbon Se Systèmes multicouche carbone-silicium
EP2472655A1 (fr) * 2006-12-15 2012-07-04 Tokyo Ohka Kogyo Co., Ltd. Elément de base d'électrode négative
US8277974B2 (en) 2008-04-25 2012-10-02 Envia Systems, Inc. High energy lithium ion batteries with particular negative electrode compositions
US8426052B2 (en) 2009-05-08 2013-04-23 Robert Bosch Gmbh Li-ion battery with porous anode support
US9012073B2 (en) 2008-11-11 2015-04-21 Envia Systems, Inc. Composite compositions, negative electrodes with composite compositions and corresponding batteries
US9061902B2 (en) 2009-12-18 2015-06-23 The Board Of Trustees Of The Leland Stanford Junior University Crystalline-amorphous nanowires for battery electrodes
US9139441B2 (en) 2012-01-19 2015-09-22 Envia Systems, Inc. Porous silicon based anode material formed using metal reduction
US9190694B2 (en) 2009-11-03 2015-11-17 Envia Systems, Inc. High capacity anode materials for lithium ion batteries
US9601228B2 (en) 2011-05-16 2017-03-21 Envia Systems, Inc. Silicon oxide based high capacity anode materials for lithium ion batteries
DE102015120879A1 (de) * 2015-12-02 2017-06-08 Institut Für Solarenergieforschung Gmbh Verfahren zum Herstellen einer Silizium-basierten porösen Elektrode für eine Batterie, insbesondere Lithium-Ionen-Batterie
US9780358B2 (en) 2012-05-04 2017-10-03 Zenlabs Energy, Inc. Battery designs with high capacity anode materials and cathode materials
US10020491B2 (en) 2013-04-16 2018-07-10 Zenlabs Energy, Inc. Silicon-based active materials for lithium ion batteries and synthesis with solution processing
US10290871B2 (en) 2012-05-04 2019-05-14 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
US10326131B2 (en) 2015-03-26 2019-06-18 Sparkle Power Llc Anodes for batteries based on tin-germanium-antimony alloys
US10886526B2 (en) 2013-06-13 2021-01-05 Zenlabs Energy, Inc. Silicon-silicon oxide-carbon composites for lithium battery electrodes and methods for forming the composites
US20210066693A1 (en) * 2016-02-26 2021-03-04 Apple Inc. Lithium-metal batteries having improved dimensional stability and methods of manufacture
US11094925B2 (en) 2017-12-22 2021-08-17 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance
US11476494B2 (en) 2013-08-16 2022-10-18 Zenlabs Energy, Inc. Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030138554A1 (en) * 2002-01-17 2003-07-24 Hiromasa Yagi Method for manufacturing electrode for lithium secondary battery
EP1335438A1 (fr) * 2000-09-01 2003-08-13 Sanyo Electric Co., Ltd. Electrode negative pour accumulateur au lithium et procede de production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1335438A1 (fr) * 2000-09-01 2003-08-13 Sanyo Electric Co., Ltd. Electrode negative pour accumulateur au lithium et procede de production
US20030138554A1 (en) * 2002-01-17 2003-07-24 Hiromasa Yagi Method for manufacturing electrode for lithium secondary battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BESENHARD J O ET AL: "METALLIZED MICROPOROUS POLYPROPYLENE MEMBRANES AS A SUPPORT FOR THIN-FILM ELECTRODES" 15 April 1993 (1993-04-15), JOURNAL OF POWER SOURCES, ELSEVIER, AMSTERDAM, NL, PAGE(S) 493-498 , XP000412936 ISSN: 0378-7753 abstract page 494, line 14 - page 495, line 16 figure 2 *

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9105929B2 (en) 2006-12-15 2015-08-11 Tokyo Ohka Kogyo Co., Ltd. Negative electrode base member
EP2472655A1 (fr) * 2006-12-15 2012-07-04 Tokyo Ohka Kogyo Co., Ltd. Elément de base d'électrode négative
US8927147B2 (en) 2006-12-15 2015-01-06 Kanto Gakuin School Corporation Negative electrode base member
US20130252099A1 (en) * 2006-12-15 2013-09-26 Kanto Gakuin University Surface Engineering Research Institute Negative electrode base member
US8551651B2 (en) 2006-12-15 2013-10-08 Tokyo Ohka Kogyo Co., Ltd. Secondary cell having negative electrode base member
FR2910721A1 (fr) * 2006-12-21 2008-06-27 Commissariat Energie Atomique Ensemble collecteur de courant-electrode avec des cavites d'expansion pour accumulateur au lithium sous forme de films minces.
EP1936722A3 (fr) * 2006-12-21 2009-01-14 Commissariat à l'Energie Atomique Accumulateur au lithium comprenant un ensemble collecteur de courant-électrode avec des cavités d'expansion et procédé de fabrication
EP1936722A2 (fr) * 2006-12-21 2008-06-25 Commissariat à l'Energie Atomique Accumulateur au lithium comprenant un ensemble collecteur de courant-électrode avec des cavités d'expansion et procédé de fabrication
US7816031B2 (en) 2007-08-10 2010-10-19 The Board Of Trustees Of The Leland Stanford Junior University Nanowire battery methods and arrangements
US8877374B2 (en) 2007-08-10 2014-11-04 The Board Of Trustees Of The Leland Stanford Junior University Nanowire battery methods and arrangements
US8673490B2 (en) 2008-04-25 2014-03-18 Envia Systems, Inc. High energy lithium ion batteries with particular negative electrode compositions
US8277974B2 (en) 2008-04-25 2012-10-02 Envia Systems, Inc. High energy lithium ion batteries with particular negative electrode compositions
US9012073B2 (en) 2008-11-11 2015-04-21 Envia Systems, Inc. Composite compositions, negative electrodes with composite compositions and corresponding batteries
US8426052B2 (en) 2009-05-08 2013-04-23 Robert Bosch Gmbh Li-ion battery with porous anode support
US8329327B2 (en) 2009-05-08 2012-12-11 Robert Bosch Gmbh Li-ion battery with variable volume reservoir
WO2010129866A1 (fr) * 2009-05-08 2010-11-11 Robert Bosch Gmbh Batterie lithium-ion avec réservoir à volume variable
US10003068B2 (en) 2009-11-03 2018-06-19 Zenlabs Energy, Inc. High capacity anode materials for lithium ion batteries
US9190694B2 (en) 2009-11-03 2015-11-17 Envia Systems, Inc. High capacity anode materials for lithium ion batteries
US11309534B2 (en) 2009-11-03 2022-04-19 Zenlabs Energy, Inc. Electrodes and lithium ion cells with high capacity anode materials
US9061902B2 (en) 2009-12-18 2015-06-23 The Board Of Trustees Of The Leland Stanford Junior University Crystalline-amorphous nanowires for battery electrodes
WO2012084570A1 (fr) * 2010-12-21 2012-06-28 Sgl Carbon Se Systèmes multicouche carbone-silicium
US9601228B2 (en) 2011-05-16 2017-03-21 Envia Systems, Inc. Silicon oxide based high capacity anode materials for lithium ion batteries
US9139441B2 (en) 2012-01-19 2015-09-22 Envia Systems, Inc. Porous silicon based anode material formed using metal reduction
US11502299B2 (en) 2012-05-04 2022-11-15 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
US10553871B2 (en) 2012-05-04 2020-02-04 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
US10290871B2 (en) 2012-05-04 2019-05-14 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
US9780358B2 (en) 2012-05-04 2017-10-03 Zenlabs Energy, Inc. Battery designs with high capacity anode materials and cathode materials
US11387440B2 (en) 2012-05-04 2022-07-12 Zenlabs Energy, Inc. Lithium ions cell designs with high capacity anode materials and high cell capacities
US10686183B2 (en) 2012-05-04 2020-06-16 Zenlabs Energy, Inc. Battery designs with high capacity anode materials to achieve desirable cycling properties
US10020491B2 (en) 2013-04-16 2018-07-10 Zenlabs Energy, Inc. Silicon-based active materials for lithium ion batteries and synthesis with solution processing
US10886526B2 (en) 2013-06-13 2021-01-05 Zenlabs Energy, Inc. Silicon-silicon oxide-carbon composites for lithium battery electrodes and methods for forming the composites
US11646407B2 (en) 2013-06-13 2023-05-09 Zenlabs Energy, Inc. Methods for forming silicon-silicon oxide-carbon composites for lithium ion cell electrodes
US11476494B2 (en) 2013-08-16 2022-10-18 Zenlabs Energy, Inc. Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics
US10326131B2 (en) 2015-03-26 2019-06-18 Sparkle Power Llc Anodes for batteries based on tin-germanium-antimony alloys
DE102015120879A1 (de) * 2015-12-02 2017-06-08 Institut Für Solarenergieforschung Gmbh Verfahren zum Herstellen einer Silizium-basierten porösen Elektrode für eine Batterie, insbesondere Lithium-Ionen-Batterie
US20210066693A1 (en) * 2016-02-26 2021-03-04 Apple Inc. Lithium-metal batteries having improved dimensional stability and methods of manufacture
US11784302B2 (en) * 2016-02-26 2023-10-10 Apple Inc. Lithium-metal batteries having improved dimensional stability and methods of manufacture
US11094925B2 (en) 2017-12-22 2021-08-17 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance
US11742474B2 (en) 2017-12-22 2023-08-29 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance

Also Published As

Publication number Publication date
WO2005076389A9 (fr) 2005-10-27
WO2005076389A3 (fr) 2006-05-04

Similar Documents

Publication Publication Date Title
Patil et al. Issue and challenges facing rechargeable thin film lithium batteries
WO2005076389A2 (fr) Anodes autoporteuses a film mince de type a alliage destinees aux batteries a ions de lithium
JP4846901B2 (ja) 電極材料およびそれを含む組成物
Ortiz et al. TiO2 nanotubes manufactured by anodization of Ti thin films for on-chip Li-ion 2D microbatteries
US6824922B2 (en) Thin film for anode of lithium secondary battery and manufacturing method thereof
US9356281B2 (en) Intercalation electrode based on ordered graphene planes
US6828063B2 (en) Anode thin film for lithium secondary battery
Kim et al. Improvement of capacity and cyclability of Fe/Si multilayer thin film anodes for lithium rechargeable batteries
KR20060066756A (ko) 리튬 2차전지용 전극 및 리튬 2차전지
Uzakbaiuly et al. Physical vapor deposition of cathode materials for all solid-state Li ion batteries: a review
JP2003077529A (ja) リチウム電池及びリチウム二次電池
JP5444771B2 (ja) 固体電解質電池および固体電解質電池の製造方法
US8647770B2 (en) Bismuth-tin binary anodes for rechargeable magnesium-ion batteries
WO2004006362A1 (fr) Pile secondaire à électrolyte non aqueux
EP1289033B1 (fr) Anode à film mince pour pile secondaire et son procédé de préparation
JP2006324210A (ja) リチウム二次電池用負極材料及びその製造方法
Myung-Hoon et al. Electrochemical characteristics of Si/Mo multilayer anode for Li ion batteries
JP4329357B2 (ja) リチウム二次電池負極部材、及びその製造方法
Nam et al. The effects of Cu-doping in V 2 O 5 thin film cathode for microbattery
CN114050309B (zh) 全固态锂离子电池、制备方法和电子装置
CN117795700A (zh) 一种制造作为锂电池用阳极的硅电极的方法
KR20180023380A (ko) 리튬이온전지 및 이의 제조방법
US20130323582A1 (en) Indium-tin binary anodes for rechargeable magnesium-ion batteries
TW202401876A (zh) 用於鋰離子電池銅電流導體上之平面矽陽極
KR20240066005A (ko) 비정질 금속 합금 코팅층을 구비하는 무음극 리튬 이차전지, 리튬금속 이차전지, 리튬 이차전지 및 전고체 이차전지

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
COP Corrected version of pamphlet

Free format text: PAGES 1/12-12/12, DRAWINGS, REPLACED BY NEW PAGES 1/12-12/12; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase